This application is the national phase under 35 U.S.C. xc2xa7371 of PCT International Application No. PCT/EP98/07830 which has an International filing date of Dec. 2, 1998, which designated the United States of America.
The invention relates to storage-stable, cationically polymerisable preparations which have improved curing behaviour. The preparations are based on compounds containing epoxy groups and/or N-alkyl aziridino groups and/or vinyl ether groups.
It is well known that the polymerisation of cationically polymerisable compounds may be initiated by substances with acid properties (H.-G. Elias, xe2x80x9cMakromolekxc3xclexe2x80x9d, Hxc3xcthig u. Wepf Verlag (1990)).
It is thus known from U.S. Pat. No. 3,842,019 that sulfonic acid salts such as, for example, CF3SO3Ag may be used as latent catalysts for the curing or polymerisation of cationically sensitive monomers, such as, for example, epoxides, vinyl ethers, N-vinyl compounds, aziridines, ethylenically unsaturated hydrocarbons and acetals.
Moreover, curable epoxy compositions are known from EP-A-0 083 130 which contain a metal salt catalyst corresponding to the formula M(XFn)p as hardener, wherein M is lithium or a metal of group II, X means boron, arsenic, antimony or phosphorus, n is equal to 4 if n means boron and n is 6 if X means arsenic, antimony or phosphorus, and p is 1 if M means lithium and 2 if M is a metal of group II. The metal salt catalysts are incorporated in the curable composition in a pre-prepared catalyst composition.
Finally, curable epoxy resins are known from JP-A-52080399 which contain imidazolium salts and anion acceptors, such as, for example, metals, carboxylic acid salts of metals, etc., for improving curing.
It is important for the use of cationically polymerisable preparations that polymerisation begins at the desired time and is ended with a curing pattern that depends on the application in question.
For the production, storage and use of cationically polymerisable preparations, it is necessary to prevent unwanted premature polymerisation and to obtain the desired pattern of the degree of conversion/time curve after initiation.
The object is achieved by cationically polymerisable preparations which are characterised in that they contain 0.0005 to 50 wt. % of soluble and/or fine-particle organic and/or inorganic alkaline earth and/or alkali metal compounds.
Surprisingly, it was ascertained that the retarding effect of the soluble and/or fine-particle organic and/or inorganic alkaline earth and/or alkali metal compounds is greatly reduced as polymerisation proceeds. This retarding effect at the beginning of cationic polymerisation and its reduction as polymerisation proceeds may be utilised both to prolong the pot life once initiation has taken place and to produce storage-stable cationically polymerisable preparations without the disadvantage of a reduced degree of conversion. The use according to the invention of the above-mentioned alkaline earth and/or alkali compounds permits the production of storage-stable cationically polymerisable preparations and, moreover, adjustment of the curing pattern and, more particularly, of the pot life of the initiated preparation at ambient temperature and of the time required to achieve further processability of the cured material.
The cationically polymerisable compounds according to the invention are based preferably on monomers containing epoxy groups and/or N-alkyl aziridino groups and/or vinyl ether groups.
Suitable monomers containing epoxy groups are aromatic, aliphatic and cycloaliphatic epoxy compounds. Typical representatives of said monomers are the glycidyl ethers of bisphenols or novolaks and of aliphatic alkanols, alkane diols or polyether diols.
The monomers containing cycloaliphatic epoxy groups are selected preferably from the group (1) comprising the diepoxides of cycloaliphatic esters having the general structure 
wherein the substituents R1 to R18 may be the same or different and independently of one another mean H, alkyl with 1 to 12 carbon atoms or aryl with 6 to 15 carbon atoms, (2) comprising products of the reaction of epoxidised cyclohexane derivatives of the alcohol and acid type with aliphatic dicarboxylic acids or diols and (3) comprising cycloaliphatically substituted dioxyspiro alkanes.
Cycloaliphatic diepoxy compounds used in particular preference are 3,4-epoxycyclohexylmethanol-3xe2x80x2,4xe2x80x2-epoxycyclohexylcarboxylate and 3-(3xe2x80x2,4xe2x80x2-epoxycyclo-(hexyl)-8,9-epoxy-2,4-dioxyspiro(5,5)undecane.
These and other cycloaliphatic diepoxides which may be used according to the invention are described, for example, in EP-B-0 119 425.
The production and cationic polymerisation of N-alkylaziridino compounds is by no means new and is summarised by H. Bestian in xe2x80x9cMethoden der Organischen Chemiexe2x80x9d (Houben Weyl) XII/1 (1958). DE-C-17 45 810 describes the synthesis of aziridino polyethers and the production of moulded articles on the basis of cationic polymerisation of said aziridino polyethers. Aziridino polyethers are used in dental preparations and, more particularly, in impression materials.
The cationic polymerisability of vinyl ethers is by no means new and is utilised nowadays for surface treatment, for example, in coating compounds with very high reactivity. Typical representatives of monomeric vinyl ethers are: monovinyl ethers of aliphatic, branched and unbranched alcohols such as n-butylvinyl ether, octadecylvinyl ether, cyclohexylvinyl ether, tert.-amylvinyl ether, butane diol monovinyl ether, divinyl ethers of ethylene glycol and various oligoethylene glycols, and hexane diol and trivinyl ethers of trimethylol propane.
The types mentioned and individual representatives of cationically polymerisable monomers may be used on their own and in mixture.
When making a selection, however, both the differing reactivity and the complicating factor that cationic polymerisation may take place at different calionic centres have to be taken into account.
The preparations according to the invention also contain the compounds suitable for initiating polymerisation. Depending on the number of components into which the preparations have to be divided up in order to obtain sufficient storage stability, and depending on the properties of the monomers, various classes of compounds may be considered.
Using soluble and/or fine-particle organic and/or inorganic alkaline earth and/or alkali compounds according to the invention, it is possible to produce one-component storage-stable preparations containing both the individual monomers described or mixtures of individual types of monomers and individual representatives as well as photoinitiators of the onium compound and/or metallocenium compound typexe2x80x94in each case with a complex anion having a weak nucleophilic effect.
Typical representatives of onium compounds which decompose on irradiation with light in a wave length from 280 to 400 nm are bisaryliodonium compounds and trisarylsulfonium compounds.
The metallocenium cation may have a variety of structures, as shown, for example, in EP-A-0 542 716. For use in the materials according to the invention, however, it is expedient to select those cations which decompose to form Lewis acids or Brxc3x6nsted acids on irradiation with light in a wave length from 300 to 550 nm. This condition may be fulfilled in an industrially useful manner by metallocenium compounds with iron as the central atom.
The anions used may be, for example, the hexafluorophosphate or the hexafluoroantimonate anion. Also suitable are complex borate anions having the general structure 
wherein the substituents A, E, C, D may be the same or different and mean aryl or perfluoroaryl. An anion used in preference is tetrakis(pentafluorophenyl)borate.
The compounds used as photoinitiators are used preferably in concentrations from 0.1 to 2 wt. %, particularly preferably 0.4 to 1.0 wt. %, of the preparations in question.
The one-component preparations containing alkaline earth and/or alkali compounds according to the invention are characterised by good storage stability, which may be adjusted to values between 12 and 60 months at 23xc2x0 C. by means of the nature and concentration of the alkaline earth and/or alkali compounds.
If necessary from a technological angle, the duration of the retardation period after irradiation of the preparations at the start of polymerisation may be adjusted to the desired value by means of the nature and concentration of the alkaline earth and/or alkali compounds. The required curing rate after retardation can be achieved by a sufficient photoinitiator concentration and optionally by the use of moderately elevated temperatures. By adding alkaline earth and/or alkali compounds is it thus possible to formulate one-component, cationically curing preparations which have sufficient storage stability and whose curing pattern may be adjusted to the application in question.
The cationically polymerisable preparations may be divided into two partial preparations, the so-called catalyst component containing the polymerisation-initiating species, optionally in a diluent, and the so-called base component containing the monomers. The alkaline earth and/or alkali compounds to be used according to the invention may be added both to the catalyst component and to the base component. The addition to the base component is the preferred embodiment.
In principle, Brxc3x6nsted and/or Lewis acids may be used in the catalyst component in the case of a two-component embodiment. Suitable acids are, for example, hexafluoroantimonic acid, hexafluorophosphoric acid, tetrafluoroboric acid, p-toluenesulfonic acid, benzenesulfonic acid and alkane sulfonic acids.
It is also possible, however, to use systems whose individual components are divided into partial preparations and which, when the partial preparations are mixed, produce the actual polymerisation-initiating species such as, for example, the acids. For example, non photosensitive sulfonium compounds as described in DE-A-25 15 593 may be used in the catalyst component, which, after contact with the aziridino compound of the base component, form a polymerisation-initiating species of the aziridinium salt type.
Moreover, the catalyst component may contain aziridinium salts which are suitable for initiating cationic polymerisation of the appropriately selected monomers. Suitable aziridinium salts may be obtained by reaction of aziridino compounds with the above-mentioned acids.
The cationically curing, one-component or two-component preparations contain, according to the invention, 0.0005 to 50 wt, % of alkaline earth and/or alkali compounds.
The alkaline earth and alkali metal compounds may be introduced in the dissolved and in the fine-particle solid form into the preparations. It is also possible according to the invention to use inorganic fillers doped with alkaline earth and/or alkali metal compounds or containing alkaline earth and/or alkali ions, such as silicates, quartz, diatomaceous earth or fine-particle organic polymers which contain alkali compounds in the adsorbed form or the alkali metal ions in the bound form.
Soluble organic and/or inorganic alkaline earth and/or alkali metal compounds with molecular weights below 1000 g/mole are used preferably in an amount from 0.01 to 20 wt. %. Moreover, the use of high polymer compounds in an amount from 1 to 50 wt. % with an alkaline earth and/or alkali content from 0.01 to 10 wt. % is preferred.
The use of alkali metal alkyl compounds such as, for example, butyllithium is possible. It is preferable, however, to use alkaline earth and/or alkali metal alcoholates of the kind that may be obtained by reaction of selected, preferably primary monohydric or polyhydric alcohols to the corresponding alkylates.
Typical representatives of this class of compound are: lithium-2-ethylhexylalcoholate, lithiumlauryl alcoholate, sodium alcoholate of polytetrahydrofuran diol with a molecular weight of 350 g/mole, lithium alcoholate of a mixed polyether glycol of tetrahydrofuran and ethylene oxide units with a molecular weight from 3000 to 8000 and preferably 6000 g/mole.
A particularly preferred class of compound of alkaline earth and alkali compounds is that of the alkaline earth and/or alkali salts of saturated or unsaturated carboxylic acids, which carboxylic acids may be mono or polyvalent and aliphatic, olefinic or aromatic. Typical representatives of this class of compound are: calcium stearate, calcium oleate, strontium oleate, lithium-2-ethylhexanolate, sodium palmitate, sodium stearate, potassium erucate, sodium ricinolate, lithium oleate, lithium dodecyl benzoate. This class of compound also includes the alkaline earth and/or alkali metal carboxylates of saturated or unsaturated carboxylic acids which may be obtained from oligomeric monovalent and preferably polyvalent acids and the corresponding hydroxides, alkyls or alkoxides. All these compounds are used in amounts from preferably 0.01 to 20 wt. %.
Such oligomeric acids may be, for example, carboxyl-functionalised polyethers, polyesters or acrylonitrile-butadiene copolymers with molecular weights from 500 to 5000 g/mole. Alkali carboxylates which may be used to advantage because they are freely soluble in the base paste may be obtained from polyether or polyester polyols by complete or partial reaction of the OH groups with the anhydride of a divalent acid followed by neutralisation with alkali hydroxides, alkali alkyls or alkali alkoxides.
A typical representative of this class of compounds is the reaction product of a caprolactone triol with the molecular weight 540 g/mole with maleic anhydride in the ratio of OH groups to anhydride groups of 1:0.4, which is subsequently converted with lithium hydroxide or lithium alkoxide to the lithium carboxylate.
Moreover, 0.01 to 20 wt. % of alkaline earth and/or alkaline earth salts of the reaction products of cyclic anhydrides with mono and/or polyhydric alcohols are used in preference, maleic anhydride being the preferred cyclic anhydride and triols with molecular weights above 500 g/mole being preferred polyhydric alcohols for the reaction. In preference, the reaction of the OH groups of the triols with maleic anhydride takes place only partially.
Preferred alkali metal compounds are those of potassium, sodium and/or lithium, more particularly lithium. Preferred alkaline earth metal compounds are those of calcium and strontium.
The alkaline earth and/or alkali compounds adsorbed on a solid or the fillers containing alkaline earth and/or alkali ions are introduced in portions into the base component preferably towards the end of the mixing process. The addition of some alcoholates or carboxylates takes place advantageously as a pre-prepared paste.
For example, calcium stearate, calcium oleate, sodium palmitate, lithium ricinolate, lithium erucate or lithium oleate may be kneaded in polyether glycols optionally with the addition of water and brought to a pasty consistency by means of a dissolver or in a roll mill.
The addition of these retarder pastes may be carried out at any time during base component production, but is carried out advantageously towards the end of kneading.
The invention is explained in more detail on the basis of the examples below.
The preparations according to the invention may be used for bonding, sealing, casting and coating substrates, also in medical dental and technical dental preparations, and for making impressions of articles and, more particularly, for making dental impressions.